Li Zhenyu, Jiang Kunhong, Yang Yue, Pian Yijing, Liu Huizhen, Zheng Zexuan, Wang Xiyang, Jana Subhajit, Li Jiefei, Ma Zhuoyuan, Qiao Xiaoyun, Zou Xiaoxin, Ma Xuelu, Zhang Bin, Chu Haibin, Wu Yimin A
Inner Mongolia Key Laboratory of Rare Earth Catalysis, Inner Mongolia Engineering and Technology Research Center for Catalytic Conversion and Utilization of Carbon Resource Molecules, School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China.
College of Materials Science and Engineering, Jilin University, Changchun 130022, China.
Sci Adv. 2025 Jul 18;11(29):eadw4927. doi: 10.1126/sciadv.adw4927. Epub 2025 Jul 16.
Glycerol oxidation reaction (GOR) represents an economical pathway for transforming renewable feedstock to value-added chemicals. However, the inertness of C(sp)─H bonds of glycerol and intermediates results in the high energy barrier of the dehydrogenation step, relating to poor product selectivity at high glycerol conversion. Here, a carbon nanotube-supported PdBO@Pd heterostructure catalyst (PdBO@Pd/CNTs) was synthesized in which in situ-exsoluted PdBO clusters covalently covered Pd nanoparticles, thus yielding strong electronic interaction between Pd nanoparticles and PdBO clusters. The strong electronic interaction in PdBO@Pd/CNTs induces the hybridization between Pd(d), B(s, p), and O(s, p) atom orbits, optimizing the adsorption of reactants and intermediates, thus enhancing the activity for the GOR. The density functional theory calculation result reveals that the strong electronic interaction in PdBO@Pd/CNTs facilitates the hydrogen transfer in the primary C─H bond of the CHOHCHOHCHO* intermediate, thus reducing the energy barrier of the rate-determining step and improving glyceric acid selectivity toward the GOR.
甘油氧化反应（GOR）是将可再生原料转化为高附加值化学品的一种经济途径。然而，甘油及其中间体的C(sp)─H键的惰性导致脱氢步骤的高能垒，这与高甘油转化率下较差的产物选择性有关。在此，合成了一种碳纳米管负载的PdBO@Pd异质结构催化剂（PdBO@Pd/CNTs），其中原位析出的PdBO簇共价覆盖在Pd纳米颗粒上，从而在Pd纳米颗粒和PdBO簇之间产生强烈的电子相互作用。PdBO@Pd/CNTs中的强电子相互作用诱导了Pd(d)、B(s, p)和O(s, p)原子轨道之间的杂化，优化了反应物和中间体的吸附，从而提高了GOR的活性。密度泛函理论计算结果表明，PdBO@Pd/CNTs中的强电子相互作用促进了CHOHCHOHCHO*中间体一级C─H键中的氢转移，从而降低了速率决定步骤的能垒，并提高了GOR对甘油酸的选择性。
